Fundamental Concepts in Heterogeneous Catalysis

This book is based on a graduate course and suitable as a primer for any newcomer to the field, this book is a detailed introduction to the experimental and computational methods that are used to study how solid surfaces act as catalysts.   Features include: First comprehensive description of modern theory of heterogeneous catalysis Basis for understanding and designing experiments in the field   Allows reader to understand catalyst design principles Introduction to important elements of energy transformation technology Test driven at Stanford University over several semesters

Preface viii 1 Heterogeneous Catalysis and a Sustainable Future 1 2 The Potential Energy Diagram 6 2.1 Adsorption, 7 2.2 Surface Reactions, 11 2.3 Diffusion, 13 2.4 Adsorbate–Adsorbate Interactions, 15 2.5 Structure Dependence, 17 2.6 Quantum and Thermal Corrections to the Ground-State Potential Energy, 20 3 Surface Equilibria 26 3.1 Chemical Equilibria in Gases, Solids, and Solutions, 26 3.2 The Adsorption Entropy, 31 3.3 Adsorption Equilibria: Adsorption Isotherms, 34 3.4 Free Energy Diagrams for Surface Chemical Reactions, 40 Appendix 3.1 The Law of Mass Action and the Equilibrium Constant, 42 Appendix 3.2 Counting the Number of Adsorbate Configurations, 44 Appendix 3.3 Configurational Entropy of Adsorbates, 44 4 Rate Constants 47 4.1 The Timescale Problem in Simulating Rare Events, 48 4.2 Transition State Theory, 49 4.3 Recrossings and Variational Transition State Theory, 59 4.4 Harmonic Transition State Theory, 61 5 Kinetics 68 5.1 Microkinetic Modeling, 68 5.2 Microkinetics of Elementary Surface Processes, 69 5.3 The Microkinetics of Several Coupled Elementary Surface Processes, 74 5.4 Ammonia Synthesis, 79 6 Energy Trends in Catalysis 85 6.1 Energy Correlations for Physisorbed Systems, 85 6.2 Chemisorption Energy Scaling Relations, 87 6.3 Transition State Energy Scaling Relations in Heterogeneous Catalysis, 90 6.4 Universality of Transition State Scaling Relations, 93 7 Activity and Selectivity Maps 97 7.1 Dissociation Rate-Determined Model, 97 7.2 Variations in the Activity Maximum with Reaction Conditions, 101 7.3 Sabatier Analysis, 103 7.4 Examples of Activity Maps for Important Catalytic Reactions, 105 7.4.1 Ammonia Synthesis, 105 7.4.2 The Methanation Reaction, 107 7.5 Selectivity Maps, 112 8 The Electronic Factor in Heterogeneous Catalysis 114 8.1 The d-Band Model of Chemical Bonding at Transition Metal Surfaces, 114 8.2 Changing the d-Band Center: Ligand Effects, 125 8.3 Ensemble Effects in Adsorption, 130 8.4 Trends in Activation Energies, 131 8.5 Ligand Effects for Transition Metal Oxides, 134 9 Catalyst Structure: Nature of the Active Site 138 9.1 Structure of Real Catalysts, 138 9.2 Intrinsic Structure Dependence, 139 9.3 The Active Site in High Surface Area Catalysts, 143 9.4 Support and Structural Promoter Effects, 146 10 Poisoning and Promotion of Catalysts 150 11 Surface Electrocatalysis 155 11.1 The Electrified Solid–Electrolyte Interface, 156 11.2 Electron Transfer Processes at Surfaces, 158 11.3 The Hydrogen Electrode, 161 11.4 Adsorption Equilibria at the Electrified Surface–Electrolyte Interface, 161 11.5 Activation Energies in Surface Electron Transfer Reactions, 162 11.6 The Potential Dependence of the Rate, 164 11.7 The Overpotential in Electrocatalytic Processes, 167 11.8 Trends in Electrocatalytic Activity: The Limiting Potential Map, 169 12 Relation of Activity to Surface Electronic Structure 175 12.1 Electronic Structure of Solids, 175 12.2 The Band Structure of Solids, 179 12.3 The Newns–Anderson Model, 184 12.4 Bond-Energy Trends, 186 12.5 Binding Energies Using the Newns–Anderson Model, 193 Index 195